EP0573636B1 - Ballistische materialien - Google Patents

Ballistische materialien Download PDF

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Publication number
EP0573636B1
EP0573636B1 EP19930900877 EP93900877A EP0573636B1 EP 0573636 B1 EP0573636 B1 EP 0573636B1 EP 19930900877 EP19930900877 EP 19930900877 EP 93900877 A EP93900877 A EP 93900877A EP 0573636 B1 EP0573636 B1 EP 0573636B1
Authority
EP
European Patent Office
Prior art keywords
smc
composite
plies
glass fibers
ballistic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19930900877
Other languages
English (en)
French (fr)
Other versions
EP0573636A1 (de
Inventor
David Randall Hartman
Ralph Bernard Jutte
Timothy Wayne Ramey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Advanced Glassfiber Yarns LLC
Original Assignee
Advanced Glassfiber Yarns LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Advanced Glassfiber Yarns LLC filed Critical Advanced Glassfiber Yarns LLC
Publication of EP0573636A1 publication Critical patent/EP0573636A1/de
Application granted granted Critical
Publication of EP0573636B1 publication Critical patent/EP0573636B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
    • C08J2361/10—Phenol-formaldehyde condensates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/911—Penetration resistant layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2615—Coating or impregnation is resistant to penetration by solid implements
    • Y10T442/2623—Ballistic resistant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2959—Coating or impregnation contains aldehyde or ketone condensation product

Definitions

  • the present invention relates to glass fiber composites articles which have ballistic resistant properties. More particularly, the invention relates to thick, self-supportable ballistic resistant composites which may be used as structural armor.
  • Ballistic resistant articles which contain high strength fibers for use as structural members and panels for a wide variety of military equipment are known.
  • U.S. Patent No. 4,842,923 discloses ballistic resistant materials formed via a prepreg process which are fire resistant, smoke-resistant, non-toxic, nonconductive, self-supporting and stiff machineable, thick and strong so as to allow their use in structural armor applications and as ballistic resistant liners.
  • a prepreg is formed by coating high strength magnesia aluminosilicate glass fibers with a solution of a partially condensed, further condensable low molecular weight product.
  • the solution contains large amounts of solvents (e.g. 25% alcohol, 10% water and excess formaldehyde) which have to be evaporated off.
  • the coated fibers are then heated to increase the resole molecular weight and thereby form the easily handleable prepreg.
  • the prepreg plies are then heated under pressure until by-product water gradually escapes. Then they are heated to an elevated temperature and held at that temperature to fully polycondense and cure the resin.
  • a plurality of plies of such prepregs will be molded to form the ballistic composites.
  • the present invention provides a method of producing a ballistic-resistant glass fiber composite by curing and condensing an essentially solventless sheet molding compound (SMC) product of phenolic resin and high strength glass.
  • the sheet molding compound includes high strength magnesia aluminosilicate glass fibers and partially condensed, further condensable, phenol formaldehyde resole reaction product formed by reacting formaldehyde and phenol in a molar ratio between 1:1 and 1.5:1.
  • the sheet molding compound is essentially alcohol free and contains up to 3 weight percent water. As a consequence it eliminates the alcohol solvent and most of the water present in the known products - it is therefore not required to drive off those products with heat, as required when forming a prepreg.
  • V 50 values in excess of 727 meters (2,400 feet) per second For example, a plurality of layers of cured and condensed SMC, having a total thickness of 12.8 mm (1 ⁇ 2 inch) and an areal density of 22.0 to 25.4 kg/m 2 (4.5 to 5.2 pounds per square foot), gave a V 50 (protection ballistic limit) value in excess of 727 m/s (2,400 ft/s) with a 2.9 g (44 grain) steel 7.6 mm (0.30 calibre) fragment-simulating projectile. Good results have been obtained with essentially no alcohol, very little water and only a slight excess of formaldehyde.
  • the SMC in flat sheet form includes a pair of flexible, outer plastic films with a moldable material or compound therebetween.
  • the SMC can be cut to approximate sizes or shapes for a given mold cavity and, after the outer sheets are removed, the compound can be used in multiple layers.
  • the molding compound can be distributed in the die or mold cavity in an approximation such that very high pressures are not required to form the completed molded product.
  • the SMC utilizes a single, common source of resin-containing material for application to both outer plastic films forming the surfaces of the SMC.
  • the resin-containing material includes a liquid resin, a catalyst, and pre-blended solids or fillers along with a mold-release material, and a thickening agent.
  • the combined and mixed material is fed to a common supply point from which it is then divided into two streams.
  • One stream is directed to an upper surface of a first one of the outer films of plastic and the other stream is directed optionally to the upper surface of the second one of the outer films of plastic, with the material uniformly spread on both sheets.
  • Reinforcing fibers are uniformly distributed over the resin-containing material on the first sheet.
  • the second sheet is directed into parallel relationship with respect to the first sheet with the resin-containing material on the second sheet moved into contact with the fibers on the first sheet.
  • the resulting composite thus has identical resin-containing layers on both of the films and it is only necessary to mix the middle layer of fibers with the two resin-containing material layer of fibers to achieve a uniform molding compound throughout the space between the outer two plastic sheets.
  • This mixing can be achieved by passing the composite between sets of rollers which knead the material and enable the fibers to be wet-out thoroughly with respect to the two resin-containing layers.
  • the upper film, or both if desired, can then be punctured to release air from the material within, with further kneading or compression applied to force out the air.
  • Heat then may be applied to continue wet-out and chemically thicken the SMC, after which the SMC can be rolled onto a reel for easy storage until ready for use.
  • the SMC can be stored anywhere from a few days to several months or longer without curing, thereby retaining the soft, pliable, non-tacky condition desired for the molding process.
  • U.S. Patent No. 3,861,982 issued in 1975 further describes equipment and processes for producing SMC.
  • Magnesia aluminosilicate glass fibers used herein are high strength fibers and typically have a tensile strength in excess of about 3.5 x 10 6 kilopascals (500,000 psi). These fibers are roughly about two-thirds by weight silica, and typically on the order of about 65% by weight silica, and one-third being magnesia and alumina with the alumina being present in a greater amount than the magnesia. Typically alumina will be about 25% by weight and magnesia about 10% by weight for outstanding results. Best results are obtained when the fibers have a water resistant, impact debondable size coating thereon.
  • Preferred size coatings are sizes containing an epoxy based film former and an epoxy silane coupling agent along with other conventional materials.
  • Preferred form of glass is a balanced woven roving configuration. Woven roving weights of 814g/m 2 (24 oz/yd 2 ) have commonly been used. Various applications have required weave weight range of 271 - 1628g/m 2 (8-48 oz/yd 2 ) and specialty woven, crossply, biaxial, triaxial, or quasi axial construction. The reinforcement form of woven roving or otherwise assembled fabric or mat maintains ballistic performance in final part and also allows proper consolidation, fiber orientation, and fiber conformity to complex shapes under both compression and vacuum bag molding conditions. Other suitable forms include specialty mats and weaves, crossply biaxial, triaxial, and quasi axial assemblies.
  • the phenol formaldehyde resin is a resole phenolic.
  • the molar reactant ratio of formaldehyde to phenol is between about 1:1 to about 3:1, with best results beings obtained from 1.1:1 to 1.6:1.
  • formaldehyde to phenol ratio's between 1.1:1 to less than 1.5:1 work best in our SMC.
  • the number of SMC plies which are molded will generally be sufficient to form a final composite product having an areal density of at least about 12.2 kg per square meter (2.5 pounds per square foot).
  • the number of SMC plies which are molded will generally be sufficient to form a final composite product having an areal density of at least about 12.2 kg per square meter (2.5 pounds per square foot).
  • Satisfactory vehicle spall liners are produced by using a sufficient number of plies to produce areal density of an excess of about 19 kg/m 2 (3.9 pounds per square foot) and about 25.4 kg per square meter (5.2 pounds per square foot).
  • the ballistic resistant panels of this invention will have a thickness on the order of at least about 6.4 millimeter (1/4 inch) and may be as thick as 76.2 mm (3 inches or more).
  • a plurality of SMC plies will be molded to form composites having an areal density greater than at least about 12.2 kg per square meter (2.5 pounds per square foot).
  • the laminated composite panels formed in accordance with the present invention when formed to a thickness of the order of about 12.8 mm (1/2 inch) with an areal density between about 22.0 kg per square meter (4.5 pounds per square foot) to about 25.4 kg per square meter (5.2 pounds per square foot), will have a V 50 value (protection ballistic limit) of in excess of about 727 meters (2,400 feet) per second up to as high as 868 meters (2,865 feet) per second or even higher (with 44 grain steel 0.30 caliber fragment simulating projectiles).
  • the SMC is produced using reinforcement input of a 841g/m 2 (24 oz/yd 2 ) woven roving made with a balanced plain weave construction form S-2 Glass® 463AA250 roving.
  • the Borden SL359 resole phenolic resin is metered uniformly onto the bottom plastic processing film using a doctor blade or knife edge coater which is set at about an uniform 20 mil opening.
  • the woven roving is continuously dispensed onto the bottom coated film, and conveyed to where an uncoated top film is continuously applied to the top surface.
  • the SMC then is conveyed to a double chain link belt compaction section that is applying compression pressure to force the resin into the woven roving, while moving in a serpentine mode to work the glass for improved wet-out.
  • the SMC passes over an inspection station to transmit light through the layered film to assure uniform impregnation has been achieved by proper alignment of knife edge impregnation has been achieved by proper alignment of knife edge coater and compaction.
  • the pre-tensioned SMC is rolled up by a standard SMC turret. The roll configuration is preferred to maintain good contact of resin coated film with the reinforcement to allow further wicking of resin into the woven roving at either room temperature or up to 32°C (90°F).
  • the SMC is then stored until required for molding.
  • the SMC can be molded flat, curvilinear, or to complex tooling in a hydraulic compression molding press following process conditions described in prior Patent No. 4,842,923 issued in 1989.
  • This low advanced SMC also provides the opportunity to mold in an alternate process referred to as vacuum bagging.
  • Conventional phenolic prepreg would normally be to far advanced in cure to allow molding in a low pressure, vacuum forming method.
  • the SMC compound is of a pliable nature and can be placed by hand or machine into a complex shape (other than a flat configuration), consolidated and cured using state-of-the-art vacuum forming technology. Care must be given to the selection of heat/moisture resistant films or the use of an elastomeric forming bag for molding this material.
  • Mold time and temperature can be adjusted to part thickness and mass such that full consolidation and removal of condensation can occur similar to the cure and performance established in prior Patent No. 4,842,923.
  • the present invention describes an SMC fiber glass composite of a high strength magnesia aluminosilicate glass fibers and a phenol formaldehyde condensation product as the matrix resin.
  • the composite has a high resistance to penetration by ballistic penetrants and can be used for armor or as a spall liner for military vehicles, ship and aircraft.
  • the composite also has a high structural ability and can be used for vehicle subcomponents such as a turret or as the vehicle structural hull.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)

Claims (7)

  1. Verfahren zur Herstellung eines schußhemmenden Verbundmaterials, aufweisend:
    Bereitstellen einer formbaren Zusammensetzung, die im wesentlichen alkoholfrei ist und bis 3 Gew.-% Wasser sowie ein teilweise kondensiertes, weiter kondensierbares Phenol-Formaldehyd-Resolharz enthält, indem Formaldehyd und Phenol bei einem Molverhältnis von zwischen etwa 1:1 und 1,5:1 in Abwesenheit eines Lösungsmittels miteinander reagieren gelassen werden,
    Verteilen hochfester Magnesiumoxid-Aluminosilikat-Glasfasern zwischen Lagen der formbaren Zusammensetzung, um eine Harzmatte (SMC) zu bilden,
    Stapeln mehrerer SMC-Schichten in einer Form,
    Formen der Schichten während einer zur im wesentlichen völligen Polykondensation und Aushärtung des Phenol-Formaldehyd-Reaktionsprodukts und Bildung eines schußhemmenden Verbundmaterials gewünschter Dicke ausreichenden Zeitspanne.
  2. Verfahren nach Anspruch 1, wobei das Verbundmaterial durch Druckformen mehrerer SMC-Schichten gebildet wird.
  3. Verfahren nach Anspruch 1, wobei das Verbundmaterial durch Vakuumformen mehrerer SMC-Schichten gebildet wird.
  4. Verfahren nach einem der Ansprüche 1 bis 3 mit einem Erhitzen der SMCs vor dem Stapeln in einer Form, um die SMC weiter zu benetzen und chemisch zu verdicken.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei die Glasfasern ein Textilerzeugnis oder eine Matte darstellen.
  6. Verfahren nach Anspruch 5, wobei die Glasfasern ein Roving-Gewebe darstellen.
  7. Verfahren nach einem der Ansprüche 1 bis 6, wobei auf den Glasfasern ein wasserbeständiger, Stoß-lösbarer Schlichte-Überzug vorhanden ist.
EP19930900877 1991-12-26 1992-12-10 Ballistische materialien Expired - Lifetime EP0573636B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US07/813,616 US5215813A (en) 1991-12-26 1991-12-26 Ballistic materials
US813616 1991-12-26
PCT/US1992/010489 WO1993013163A1 (en) 1991-12-26 1992-12-10 Ballistic materials

Publications (2)

Publication Number Publication Date
EP0573636A1 EP0573636A1 (de) 1993-12-15
EP0573636B1 true EP0573636B1 (de) 1999-11-03

Family

ID=25212915

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19930900877 Expired - Lifetime EP0573636B1 (de) 1991-12-26 1992-12-10 Ballistische materialien

Country Status (12)

Country Link
US (1) US5215813A (de)
EP (1) EP0573636B1 (de)
JP (1) JPH06509384A (de)
KR (1) KR100249395B1 (de)
CN (1) CN1074857A (de)
AU (1) AU3239593A (de)
DE (1) DE69230252T2 (de)
DK (1) DK0573636T3 (de)
ES (1) ES2139648T3 (de)
MX (1) MX9207544A (de)
WO (1) WO1993013163A1 (de)
ZA (1) ZA929724B (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU645739B3 (en) * 1993-08-19 1994-01-20 Martial Armour Pty Limited Bullet resistant material
US5578359A (en) * 1994-11-29 1996-11-26 Hewlett Packard Company Magnetic shielding garment for electro-biologic measurements
DE19653218C1 (de) * 1996-12-19 1998-07-30 Bps Bowas Protection Systems G Durchschußhemmendes und schlagresistentes Schichtmaterial
US5851932A (en) * 1997-10-06 1998-12-22 Isorco, Inc. Ballistic armor laminate
US6890638B2 (en) 2002-10-10 2005-05-10 Honeywell International Inc. Ballistic resistant and fire resistant composite articles
US20040216595A1 (en) * 2003-03-17 2004-11-04 Dickson Lawrence J. Formed metal armor assembly
US8689671B2 (en) 2006-09-29 2014-04-08 Federal-Mogul World Wide, Inc. Lightweight armor and methods of making
CN101153115B (zh) * 2007-09-17 2011-06-01 王琳 用于打击乐器用敲击工具的组合物及用其制备敲击工具的方法
CN103471467A (zh) * 2013-09-03 2013-12-25 辽宁保利特种车辆有限公司 拱形复合合金护板模块及其生产工艺

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4894292A (en) * 1985-05-13 1990-01-16 Reichhold Chemicals Inc. Thermosetting phenolformaldehyde sheet molding compositions and method of preparation
US4620860A (en) * 1985-07-23 1986-11-04 Manville Corporation Process for making glass fiber products and product produced
US4842923A (en) * 1987-07-27 1989-06-27 Owens-Corning Fiberglas Corporation Ballistic materials
US5006293A (en) * 1989-02-02 1991-04-09 Owens-Corning Fiberglas Corporation Process for forming flat plate ballistic resistant materials
JPH03189110A (ja) * 1989-12-20 1991-08-19 Sumitomo Bakelite Co Ltd 成形材料の製造方法

Also Published As

Publication number Publication date
AU3239593A (en) 1993-07-28
KR100249395B1 (ko) 2000-03-15
DE69230252D1 (de) 1999-12-09
ZA929724B (en) 1993-06-14
MX9207544A (es) 1993-07-01
EP0573636A1 (de) 1993-12-15
ES2139648T3 (es) 2000-02-16
DE69230252T2 (de) 2000-05-31
WO1993013163A1 (en) 1993-07-08
US5215813A (en) 1993-06-01
CN1074857A (zh) 1993-08-04
JPH06509384A (ja) 1994-10-20
DK0573636T3 (da) 2000-04-25

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